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Rev.Adv.Mater.Sci. 17(2008) 42-61 Smita Badur and Rubina Chaudhary

UTILIZATION OF HAZARDOUS WASTES AND


BY-PRODUCTS AS A GREEN CONCRETE MATERIAL
THROUGH S/S PROCESS: A REVIEW

Smita Badur and Rubina Chaudhary


School of Energy and Environmental Studies, Devi Ahilya University, Takshashila Campus, Khandwa Road,
Indore-452001, M.P., India
Recieved: January 08, 2008

Abstract. The disposal and treatment of hazardous industrial waste is very costly affairs for the
industries, it has been a dormant issue. The new millennium brings challenges for the civil and
environmental engineers and opportunities for research on the utilization of the solid waste and
by-products and basic properties of concrete and its materials. The recycling of waste and by-
products attracts an increasing interest worldwide due to the high environmental impact of the
cement and concrete industries. Normal concrete is manufactured using sand and stones, but
lightweight concrete can be made by using industrial by-products and hazardous solid wastes
such as expanded fly ash, slag, sludge, etc. The Best Demonstrated Available Technology (BDAT)
stabilization/solidification (S/S) can be used for treatment of concrete contaminated solid hazard-
ous wastes and by-products. The performance of concrete is measured in terms of physical, engi-
neering, and chemical properties.
The review describes how chemical and mineral admixtures help in the improvement of the light-
weight concrete properties. Cement is replaced by the 15-35% fly ash in the concrete mix. Fly ash
increases concrete strength, improves sulfate resistance, decreases permeability, reduces the
water ratio required, and improves the workability of the concrete. Partial substitution solid hazard-
ous waste does not strongly affect the strength of concrete and other properties. This mixed light-
weight concrete is safe enough to be used in sustainable environmental applications, like road-
beds, filling materials, etc.

1. INTRODUCTION activated by the passage of the Resource Conser-


vation and Recovery Act (RCRA) [5]. Already ac-
Due to environmental degradation, high energy
cumulated solid wastes and increasing annual pro-
consumption, and financial constraints, various or-
duction are a major source of pollution.
ganizations in India and abroad, as well as United
In different countries, some of such wastes are
States Environmental Protection Agency (USEPA)
used for landfilling abandoned quarries and mines
have recommended various qualitative guidelines
and adopting alternative method. The hazardous
for generation, treatment, transport, handling, dis-
solids and sludges require a secure chemical land-
posal, and recycling of non-hazardous and haz-
fill. Research has been conducted to recycle valu-
ardous wastes [1–4]. It is now a global concern, to
able material and reduce the volume of hazardous
find a social, techno-economic, environmental
solid waste and other pollutants, which is harmful
friendly solution to sustain a cleaner and greener
for living organisms. For the industries, disposal of
environment. The environmental technology, dis-
sludge is very costly method, due to long-distance
posal and treatment of hazardous industrial waste
transportation and the use of illegal or question-
has been a dormant issue that has recently been
Corresponding author: Rubina Chaudhary, e-mail: rubina_chaudhary@yahoo.com

© 2008 Advanced Study Center Co. Ltd.


Utilization of hazardous wastes and by-products as a green concrete material through... 43

Fig. 1. Relationship of mix proportion with strength & W/C ratio, workability & water, cost &cement. Data
from [25].

able disposal methods. The industries are trying to The extensive use of fly ash, which is abundant
reuse solid waste material on the construction sites in India, to meet the current construction demands
[6,7]. and to decrease the environmental damage. In the
In recent years, the utilization of solid waste is past decades concrete vastly used in mega con-
the challenge for the civil and environmental engi- struction project in the country. [11]
neers to utilize economic friendly supplementary
cementitious materials produce at reasonable cost Objective of review
with the low possible environmental impact. The
use of Supplementary Cementitious Materials Review focused on utilization of industrial solid
(SCM) for e.g. Fly Ash (FA), Granulated Blast Fur- wastes and by–products (heavy metals bearing)
nace Slag (GBFS), Silica Fume (SF), Activated as concrete ingredients and also discussed the
Metakaolin (AM), etc. which can improve various mechanical and chemical properties of concrete
properties in fresh and hardened state of concrete through solidification/stabilization process.
and also increase the cost of construction. It is now
the global concern to making economic friendly ma- 2. CONCRETE
terial product at lower cost with less harmful effect Concrete is an artificial conglomerate stone made
on environment [8]. Addition of cost saving materi- essentially of Portland cement, water, sand, and
als by the replacement of considerable amount of aggregates. The mixing of all the materials is placed
cement reduces CO2 emission during the manu- into a plastic form; a chemical reaction called hy-
facturer of Portland cement [9,10]. dration takes place between the water and cement,
In India around 960 millions tonnes of solid and concrete normally changes from a plastic to a
waste is being generated annually as by-products solid state in about 2 hours. Theoretically, if kept in
during industrial, mining, municipal, agricultural, a moist environment, concrete will gain strength in
and other processes. It is important to use develop practical terms (about 90%) in the first 28 days.
technologies for the utilization of solid waste con- The product cannot be treated as concrete unless
sumption in concrete. Concrete preferred for con- all these steps are realized [14 -21].
struction, which is very durable require little or no
maintains. The assumption is largely true except
2.1. Chemistry of concrete
when it is subjected to highly aggressive environ-
ment. We build concrete structure in high polluted Concrete industry is particularly important, since it
urban and many other hostile conditions where is not only responsible for consuming natural re-
other construction materials are found to be non- sources and energy, but also for its capacity of
durable. Recently the uses of sludge in concrete absorbing other industrial waste and by-products.
have spread it to highly harsh and hostile condition
Ordinary Portland Cement + H2O + Sand + Aggre-
[11-13].
gates → Hardened Concrete + Energy (Heat)
44 Smita Badur and Rubina Chaudhary

dicalcium silicate are the same as those for


tricalcium silicate:
Dicalcium Silicate + Water → Calcium Silicate Hy-
drate + Calcium Hydroxide + Energy (Heat)
The other major components of portland ce-
ment, tricalcium aluminate and tetracalcium
aluminoferrite also react with water. Their hydra-
tion chemistry is more complicated since it involves
reactions with the gypsum as well. Because these
reactions, treated the hydration of each cement
compound independently, do not contribute signifi-
cantly to strength this statement is not completely
Fig. 2. Influence of water-cement ratio and grade
accurate. The rate of hydration of one compound
of ordinary portland cement on the 28 days com-
may be affected by varying the concentration of
pressive strength of concrete.
another. In general, the rates of hydration during
the first few days ranked from fastest to slowest
[23]:
Tricalcium aluminate > tricalcium silicate >
tetracalcium aluminoferrite > dicalcium silicate

2.2. Mix proportion of concrete


The cement used in concrete is not used as a Water, sand, and aggregate or crushed stone used
building material because it would be too expen- in concrete production in addition to cement are
sive and not as strong as concrete [22]. Concrete also abundant. With all of these raw materials, the
can sometimes contain other substances; such as distance and quality of the sources have a big im-
fly ash from industrial smoke stacks, which can pact on transportation energy use, water use for
change its properties. washing, and dust generation [24].
When water is added to cement, each of the A low water-to-cement ratio is needed to
compounds undergoes hydration and contributes achieve strong concrete. It would seem therefore
to the final concrete product. Only the calcium sili- that by merely keeping the cement content high,
cates contribute to strength. Tricalcium silicate is one could use enough water for good workability
responsible for most of the early strength (first 7 and still have a low W/C (Water/Cement) ratio. The
days). Dicalcium silicate, which reacts more slowly, problem is that cement is the most expensive
contributes only to the strength at later times. The among the basic ingredients [21,25]. The dilemma
equation for the hydration of tricalcium silicate is: is easily seen in the schematic graph of Fig. 1.

Tricalcium Silicate + Water → Calcium Silicate Hy- 2.3. Ingredients of concrete


drate + Calcium Hydroxide + Energy (Heat)
2.3.1.Cement
The majority of space is filled with calcium sili-
cate hydrate. That which is not filled with the hard- Grey cement produced by us consists of Ordinary
ened hydrate is primarily calcium hydroxide solu- Portland Cement (OPC) and Portland Pozzolana
tion. The hydration will continue as long as water Cement (PPC). OPC has three principal grades
is present and there are still unhydrated compounds that are differentiated by their compressive
in the cement paste. strengths, and consist of 53, 43, and 33 OPC (Fig.2)
Dicalcium silicate also affects the strength of [21]. W/C ratio based on the grade of cement for
concrete through its hydration. Dicalcium silicate the medium strength of concrete [26] shown in fig.
reacts with water in a similar manner compared to 2. The raw materials used in cement production
tricalcium silicate, but much more slowly. The heat are widely available in great quantities. Limestone,
released is less than that by the hydration of marl, and chalk are the most common sources of
tricalcium silicate because the dicalcium silicate is calcium in cement (converted into lime through cal-
less reactive. The products from the hydration of cinations). Common sources of silicon include clay,
Utilization of hazardous wastes and by-products as a green concrete material through... 45

sand, and shale. Minimum cement content in con- Table 1. Color and water absorption in different
crete is 1 m3 [21]. type sands.

Colour Water Absorption in percent


2.3.2. Sand (fine aggregate)
The fine aggregate or sand may be natural or Blackish 0.5%
crushed. It may be available in a riverbed or in a Grey 2%
quarry. The size of sand particles varies from a Reddish 1%
maximum of 4.75 mm down to 150 micron. Good Pinkish 1.25%
sand must contain all the particles within the above Brownish 0.5%
range, that is, it should be graded sand. The sand
may be sieved through the following Indian Stan-
dard Sieves [21]: 4.75 mm, 2.36 mm, 1.18 mm,
600 micron, 300 micron, and 150 micron. The sand
may be classified as very coarse (zone I), medium
coarse (zone II), coarse (zone III), and fine (zone
IV) depending upon its grain size distribution. The
sand samples were first sieved through 4.75 mm
sieve and the larger particles were removed. River liness of aggregate. Cement paste normally bonds
sand is very fine and is not suitable for concrete better to a rough textured surface then to a smooth
work (Table 1). It may be used for plastering only surface. Angular particle and those having rough
with the addition of some coarse sand. Very coarse vesicular surface have a higher water requirement
sand is also unsuitable for concrete work. It may then rounded materials. Nevertheless, crushed and
be used with the addition of finer sand. Coarse sand natural course aggregate generally give substan-
should be used in the structural work that is, beams, tially same compressive strength for a given ce-
slabs, columns, and foundations, etc. [27]. ment factor. The angularity of the aggregate may
cause stress concretion that affects the perfor-
2.3.3. Aggregate (course aggregate) mance of concrete. Moreover, the strength of ag-
gregate and its porosity affects the mechanical
Aggregate is the solid particles that are bound to- behavior of concrete from both strength and duc-
gether by the cement paste to create the synthetic tility point of view. These effects contribute to the
rock known as concrete. Aggregates can be fine, failure pattern of concrete and determine its be-
such as sand, or coarse, such as gravel. The rela- havior under lateral pressure [21,29,30].
tive amounts of each type and the sizes of each The accuracy of aggregate measurement by
type of aggregate determine the physical proper- volume depends upon the accuracy with which the
ties of the concrete [28]. amount of “bulking”, caused by moisture in the ag-
Sand + Cement Paste = Mortar gregate, can be determined. The amount of bulk-
ing varies not only with different moisture contents
Mortar + Gravel = Concrete but also with different gradations. Fine sand, for
example, is bulked more than coarse sand by the
Amongst all the materials, which are used, ag-
same moisture content. Furthermore, moisture
gregates are very important. The quality of aggre-
content itself varies from time to time, and a small
gates is very important since they make up about
variation causes a large change in the amount of
60 to 80% of the volume of the concrete; it is im-
bulking. For these and other reasons, aggregate
possible to make good concrete with poor aggre-
should be measured by weight rather than by vol-
gates. The grading of both fine and coarse aggre-
ume whenever possible. To make grading easier,
gate is very significant because having a full range
to keep segregation low, and to ensure that each
of sizes reduces the amount of cement paste
batch is uniform, it should be stored and measured
needed. Well-graded aggregates tend to make the
coarse aggregate from separate piles or hoppers.
mix more workable as well. The bond between the
The ratio of maximum to minimum particle size
paste and aggregate tends to set an upper limit on
should not exceed 2:1 for a maximum nominal size
the strength of concrete. Bond is influenced by the
larger than 1 inch. The ratio should not exceed 3:1
surface texture, particle size and shape, and clean-
for a maximum nominal size smaller than 1 inch.
46 Smita Badur and Rubina Chaudhary

2.3.4. Admixtures of an admixture are based on the need of the con-


crete user [21].
Sometimes, other materials are incorporated into
the batch of concrete to create specific character-
istics. These additives are called admixtures 2.3.4.2. Retarders
[21,23]. Suitable materials known as admixtures Retarders are used to slow the set of concrete when
may be added to concrete mix, just before or dur- large masses must be placed and the concrete
ing mixing, to modify one or more properties of remain plastic for a long period of time to prevent
concrete in plastic or hardened state as desired. the formation of “cold joints” between one batch
Admixtures may be used for the following purposes: and the other batch of concrete. Accelerators serve
• To increase the workability to increase the rate of strength gain and to decrease
• Without changing / increasing the water content the initial setting time. This can be beneficial when
• To increase strength concrete must be placed on a steep slope with a
• To retard the initial setting time, and single form or when it is desirable to reduce the
• To increase water tightness. time period in which concrete must be protected
Admixtures are chemicals, which are added to from freezing. The best known accelerator is cal-
the mix to achieve special purposes or to meet cer- cium chloride, which acts to increase the heat of
tain construction conditions [25]. Chemical admix- hydration, thereby causing the concrete to set up
ture works as accelerator (Table 2). faster. [21,25]
Chemical admixtures: Accelerating admixtures,
retarding admixtures, water reducing admixtures, 2.3.5. Water
air entraining admixtures, and super plasticizers.
A plasticizer may be sulfonated naphthalene or The major factor controlling strength, everything
melamine formaldehyde based. else being equal, is the amount of water used per
It is necessary to select a suitable type of ad- bag of cement. Maximum strength is obtained by
mixture, quantity, and mixing procedure depend- using less amount of water, and no more, required
ing upon the other materials and requirements. Trial for the complete hydration of the cement. As pre-
mix should be prepared and tested for slump at 30 viously mentioned, however, a mix of this type may
minutes and strength 7 and 28 curing days. It is be too dry to be workable [21]. Concrete mix al-
important to note that an admixture is effective only ways contains more water than the amount required
when the aggregate are clean. It is possible that attaining maximum strength. The amount of ex-
some admixtures may not yield the desired results cess water decreases the strength of concrete. The
because of the use of particular cement and ag- specified water-cement ratio is the perfect medium
gregate, and under the given environment [31]. between the maximum possible strength of the
Chemical admixture also affected the properties concrete and the necessary minimum workability
of concrete with accelerating and retarding air and requirements.
entraining water admixture. The addition of Na2SO4 The strength of building concrete is expressed
increases the strength of concrete and the activity in terms of the compressive strength in pounds per
of Na2SO4 depends upon the curing days (3, 7, 28 square inch (psi) reached after a 7 or 28 day set-
days) and grinding [32]. ting. This is usually referred to as probable aver-
age 7 day strength and probable average 28 day
strength [33]. The degree of cement hydration in-
2.3.4.1. Superplasticizers
creased with time and temperature, but the in-
Concrete’s strength may also be affected by the crease beyond 28 days was not significant [34].
addition of admixtures. Admixtures are substances
other than the key ingredients, which are added 2.4. Grades of concrete
during the mixing process. Some admixtures add
fluidity to concrete while requiring less water to be Various grades of concrete are specified:
used. An example of an admixture that affects • Ordinary Concrete - M10, M15, M20;
strength is superplasticizer. This makes concrete • Structural Concrete - M25 to M55;
more workable or fluid without adding excess wa- • High Strength Concrete - M60 to M80 [35];
ter. A list of some other admixtures and their func- The minimum average compressive strength of
tions is given below. Note that not all admixtures M20 grade concrete (15 cm cube) at 28 days should
increase concrete strength. The selection and use be 20 MPa (20 N/mm2). The mix type 1:2:4 is com-
monly used for M15 concrete; 1:2:4 means 1 part
Utilization of hazardous wastes and by-products as a green concrete material through... 47

of cement, 2 parts of sand, and 4 parts of aggre- secondary Calcium Silicate Hydrated (CSH) gel
gate by volume. The problem is that the quality of [45].
sand and aggregate vary greatly from one place to Placing of concrete is also very important pro-
another. Therefore, the same ratio of 1:2:4 can’t cess. It is the process of transferring of fresh con-
be expected to give a good quality of concrete with crete from the mixing or conveying device to its
different types of sand and aggregate. The materi- final place in the forms. The method of placing
als should always be measured by weight to pre- should be such that segregation, displacement of
pare concrete. A richer concrete, that is, a con- forms avoided. Prior to placing loose rust must be
crete with a higher cement ratio is stronger and removed, forms must be cleaned, and hardened
more durable [20,36-40]. surfaces of previous concrete lifts must be cleaned
K. Srinivasa Rao et al. [41] showed that a High and treated appropriately [20,31,36-40].
Strength Concrete (HSC) which was develop by The strength of concrete is strongly dependent
ACI mix design method was used to achieve a mix upon the hydration reaction just discussed. Water
with a compressive strength of 60 MPa. Mix pro- plays a critical role, particularly the amount used.
portion used was 1:0.94:1.35 and W/C ratio 0.25, The strength of concrete increases when less wa-
the size and shape of concrete were cube ter is used to make concrete (Fig. 3). The hydra-
(150x15x150 and 100x100x100 mm) and cylinder tion reaction itself consumes a specific amount of
(300x150 mm). This concrete was tested by differ- water [23].
ent parameters on different ages (1, 3, 7, 28, 56,
91 Days). Small change in compressive strength 2.5.2. Durability [freezing thawing
after 28 days and no change in compressive resistance].
strength after 56 days were reported.
Durability is the ability of concrete to resist weath-
ering action, chemical attack, abrasion and/or any
2.5. ENGINEERING PROPERTIES OF
other process of deterioration. Durable concrete
CONCRETE will retain its original form, quality, and serviceabil-
2.5.1. Unconfined compressive ity when exposed to its environment. Factors re-
strength (ucs) sponsible for aggravating or deterioration of con-
crete are: freezing and thawing, aggressive chemi-
Unconfined compressive strength depends upon cal exposure, abrasion, corrosion of metals and
many factors, including the quality and proportions other materials embedded in concrete, alkali ag-
of the ingredients and the curing environment. The gregate reaction, high temperature and poor work-
most important indicator of strength is the ratio of manship [21].
the water used compared to the amount of cement. The durability of concrete refers to the extent to
Basically, the lower this ratio is, the higher the final which the material is capable of resisting deterio-
concrete strength will be. (This concept was de- ration caused by exposure to service conditions.
veloped by Duff Abrams of The Portland Cement Concrete is also strong and fireproof. Ordinary
Association in the early 1920s and is in worldwide structural concrete that is to be exposed to the el-
use today). A minimum W/C ratio (water to cement ements must be watertight and weather resistant.
ratio) of about 0.3 by weight is necessary to en- Concrete that is subject to wear, such as floor slabs
sure that the water comes into contact with all ce- and pavements, must be capable of resisting abra-
ment particles (thus assuring complete hydration). sion. The major factor that controls the durability
In practical terms, typical values are in the 0.4 to of concrete is its strength. The stronger is the con-
0.6 ranges in order to achieve a workable consis- crete, the more durable it is. The chief factor con-
tency so that fresh concrete can be placed in the trolling the strength of concrete is the water-cement
forms and around closely spaced reinforcing bars ratio. However, the character, size, and grading
[21,25]. Compressive strength depends on the (distribution of particle sizes between the largest
curing time [42,43]. Concrete showed small change permissible coarse and the smallest permissible
in compressive strength after 28 days and no fine) of the aggregate also have important effects
change after 56 days [41]. Strength enhancement on both strength and durability [25]. Both time and
of gravel reaches 97% at the 2.8% volumetric ra- temperature to bulk transport properties, which di-
tio. The roundness of aggregate assists to distrib- rectly influence concrete durability. For pavements,
ute the lateral confinement and helps the concrete permeability and durability are intimately connected
element to experience higher stress [44]. The [46].
strength is increases because the formation of
48 Smita Badur and Rubina Chaudhary

Fig. 3. Concrete strength as a function of the water to cement ratio. Data from [23].

3. UTILIZATION OF HAZARDOUS should be investigated with regard to these degra-


SOLID WASTE AND BY-PRODUCTS dation causes, mechanical properties, and micro-
structure [50].
In developing and industrial countries, large Normal concrete is made using sand and
amounts of industrial waste or by-products are stones, but lightweight concrete can be made us-
accumulated every year. Recycling of these mate- ing industrial by-products such as expanded slag,
rials is of increasing interest worldwide, due to the clay, and sludge as aggregates. It is more difficult
high environmental impact of the cement and con- to achieve high strength with weaker aggregate
crete industries [47]. For the production of cement [21,25].
and concrete, very high amount of energy is
needed. About 7% CO2 is released to atmosphere
3.1. By-products
during cement production. It has negative influence
on ecology and future of human being [11,12]. Ac- Industrial by-product (class F - fly ash, slag) can
cording to industrial ecology concept for sustain- be used in large amount as replacement material
able development, by-product of one industry may of cement in concrete. It can be added in a quan-
be a raw material for other industry. Therefore, det- tity of 10% to about 35% by weight of cement. It
rimental effects of both industries to the environ- will be very beneficial in reducing CO2 emission
ment can be reduced. Harmful effects of concrete during production of cement, preventing the global
on the environment can be reduced by producing warming [11,12]. The cement companies have the
durable concrete and effective usage of resources. necessary expertise to mix suitable quantity of fly
Industrial by-products and solid wastes can be used ash in Portland cement and blend properly [10]; fly
for this purpose [11,48]. For this reason, cost, du- ash should never be added at site. Fly ash can
rability and environmental friendliness are impor- help with our solid waste problems, and it reduces
tant criteria used in developing concrete technolo- overall energy use. While fly ash is sometimes used
gies [49]. as a source of silica in cement production, a more
Concrete elements containing industrial by- common use is in concrete mixture as a substitute
products or solid wastes as aggregate replacement,
Utilization of hazardous wastes and by-products as a green concrete material through... 49

for some of the cement. Fly ash, or pozzolan, can


W
readily be substituted for 15% to 35% of the ce- X = ,
ment in concrete mixes, according to the U.S.EPA C + KF + S
[2] (Environmental Protection Agency). For some where, X is the water to cement ratio, W - water
applications, fly ash content can be up to 70%. content, C - cement content, F - fly ash content, S
Thus, fly ash today accounts for about 9% of the - GBFS content, and K is the efficiency factor.
cement mix in concrete. Water absorption, coeffi- The cement efficiency factor of fly ash with re-
cient of water and chloride diffusion co-efficient was spect to water tightness or water permeability which
less in fly ash concrete [51]. is approximately 0.3. There is no effect of cement
If the class C fly ash is used in the concrete mix type and curing time. Efficiency factor has some
higher replacement level is possible. If the replace- effect on concrete strength formula and it is de-
ment level is more then 25%, it shows marginal pendent on curing days and percent of replace-
reduction in the strength [52,53]. The grinding of ment [55,56]. Curing temperature is important fac-
fly ash influences the strength development in con- tor increase in curing temperature yielded in com-
crete [42,43]. As with the Class C fly ash, the Class pressive strength for fly ash replacing percentages
F fly ash is also composed primarily of an amor- [42,57].
phous phase and some crystalline components that Fly ash reacts with free lime after the hydration
include alpha-quartz, Fe3O4, Al2SiO5, (Mg,Fe)2SiO4, to form calcium silicate hydrate, which is similar to
and CaO. The main difference was that Class F fly the tricalcium and dicalcium silicates formed in
ash contains no reactive crystalline reactive com- cement curing. Through this process, fly ash in-
ponent such as C3A. The acid-insoluble residue creases concrete strength, improves sulfate resis-
(89%) of the fly ash consisted virtually of the same tance, decreases permeability, reduces the water
phases detected before treatment except for CaO ratio required, and improves the workability of the
[28]: concrete. Fly ash with low sulfur and carbon con-
tain is better for concrete.
P = f / (c + f),
There are at least a dozen companies provid-
where, P is the percentage of fly ash, f = fly ash ing fly ash to concrete producers. Other industrial
content in kg, c = cement content in kg [10]. waste products, including blast furnace slag, cin-
The use of fly ash in concrete is the highest- ders, and mill scale are sometimes substituted for
volume application for fly ash. Concrete requires some of the aggregate in concrete mixes [58]. Fly
less water when fly ash is used in place of cement, ash can be introduced in concrete directly, as a
resulting in less shrinkage and cracking [53]. Ac- separate ingredient at the concrete batch plant or,
cording to U.S.EPA, 15% is a more accepted rate can be blended with the ordinary portland cement
when coal fly ash is used as a partial cement re- (OPC) to produce blended cement, usually called
placement as an admixture in concrete [2,54]. portland pozzolana cement (PPC) in India. Fly ash
C. Natarajan reported M20 and M30 grade of blended cements are produced by several cement
concrete mixes having different replacement level companies worldwide [21].
of cement with low calcium fly ash [10]. Compres-
sive strength (Rc) values at 3-28 days curing pe- 3.2. Waste materials
riod shows a fine relationship between Rc value
and the logarithm curing time for fly ash/cement Research have investigated various properties of
mortar at different temperature [42]. concrete containing by-products and waste mate-
C. D. Ati [53] carried out laboratory scale study rials such as Granulated Blast-Furnace Slag
concrete mixtures were prepared by the replace- GBFS), Fly Ash (FA), Bottom Ash (BA), Silica
ment of 50 and 70% of cement with fly ash. The Fume, Waste Glass (WG) as mineral admixture,
range of water to cement ratio was from 0.28 to aggregate replacement or binding material [59].
0.34. The concrete mixture was cured at tempera- Study on possible usage of BA and GBFS in
ture of 20 °C at 65% relative humidity. It was con- production of plain concrete elements was per-
cluded that fly ash concrete showed higher strength formed. It was reported that replacement of BA
after 28 days. The efficiency factor K was defined decreases the unit weight of briquette. Usage of
as the ratio of the mass of cement to the mass of BA makes feasible up to 30% partial replacement
the fly ash when they had equivalent effect on the of aggregate in production of briquettes. As GBFS/
water to cement ratio [55]. Sand ratio increases in paving blocks, water ab-
50 Smita Badur and Rubina Chaudhary

sorption ratio increases too, while compression sign of 2:1 with 15% fly ash was found to be the
strength and freeze–thaw resistance decreases. intermediate condition to have satisfactory com-
However, these losses are under limit values; so, pressive strength [2,62].
the standards allow up to 30% replacement ratio The addition of pozzolans or slag modified the
[50]. microstructure. The outer CSH appeared less fibril-
Heavy metals like Pb, Cd, and Cu leachate con- lar and the cement matrix was less porous at ear-
centrations were below the analytical detection limit lier ages with use of silica fume or metakaolin. The
of atomic absorption spectrophotometer (AAS). effect of this was a reduced rate of leaching of the
Higher concentrations were measured for Cr, Zn, alkali hydroxide from the pore fluid, with which the
and Fe. The quantity of Cr, Zn, and Fe leached silica fume specimen appeared to slow the expan-
tended to increase when the initial concentration sion process, but did not prevent expansion [63].
of these metals and leachate pHs were growing. Another study was performed to assess whether
For higher loading percentages, the Cr leached was the Stabilization/Solidification (S/S) technology can
above U.S. EPA limits [45]. be applied for treatment of “real” refinery oily sludge
Partial substitution (15% or 30% by mass) of contaminated by heavy metals. The performance
cement by Sewage Sludge Ash (SSA) does not of stabilized wastes is generally measured in terms
strongly affect the strength of mortars cured at 40 of leaching and extraction tests. The samples were
°C for 3- to 28-day curing periods. High sulfur con- cured at approximately 24 °C in the laboratory for
tent in SSA does not have a decisive influence on 28 days [64]. As a result, the effects of replace-
strength development. Fineness of SSA is an im- ment of cement (by mass) with three percentages
portant parameter for strength development of of fly ash and the effects of addition of natural san
SSA/cement mortars: the coarsest fraction yields fibers on the different parameters and impact
the lowest strength values. SSA showed a greater strength of fly ash concrete. San fibers belong to
or similar contribution to mechanical development the category of ‘‘natural bast fibers.’’ It is also known
than fly ashes at early ages, but they become less as “sunn hemp”. A control mixture of proportions
efficient for longer term curing. CSGr and FSGr 1:1.4:2.19 with W/Cm of 0.47. Cement was re-
increased remarkably with increasing SSA replace- placed with three percentages (35%, 45%, and
ment [60]. 55%) of class F fly ash. Three percentages of san
In this study sewage sludge was used as an fibers (0.25%, 0.50%, and 0.75%) having 25-mm
additive in order to develop new construction ma- length were used. Addition of san fibers reduced
terials. For this purpose, several mixtures of sludge the workability; did not significantly affect the com-
cement calcium chloride and calcium hydroxide pressive strength; increased the splitting tensile
were prepared and Stabilized/Solidified (S/S). Cal- strength and flexural strength, and tremendously
cium chloride and calcium hydroxide were used enhanced the impact strength of fly ash concrete
as accelerating additives. XRD and SEM studies as the percentage of fibers increased [65].
were performed to determine the hydration prod- This study also investigated the possibilities of
ucts. The specimens were tested in order to deter- plain concrete containing dry sludge. The S/S
mine their setting time and compressive strength mechanisms for sludge from treatment plants in a
after 28 days. Furthermore, in order to investigate Portland cement matrix have previously been
the environmental compatibility of these new ma- evaluated in [1, 5-7,66].
terials, Toxicity Characteristics Leaching Procedure
(TCLP) and CEN/TS 14405 tests were carried out 3.3. Admixtures
for the determination of heavy metals leaching [61].
Jarosite released from zinc metal extraction Industrial waste works with Mineral admixtures in
process is hazardous in nature. Statistically de- concrete are summarized in [67].
signed experiments on S/S sintered jarosite CCRs Mineral admixtures used in concrete were fly
products confirmed that the compressive strength ash, metakaolin, GGBS, and silica fume since
of jarosite bricks reached as high as 140 kg/cm2 many important structures built with silica fume in
with 14.5% water absorption capacity at the com- concrete are used for durability aspects [68].
bination of 3:1 ratio of jarosite and clay, respec- S. Asavapisit and D. Chotklang [45] investigated
tively, but, concentrations of all the toxic elements the potential for utilization of alkali activated (Pul-
recommended by U.S.EPA TCLP standard are not verized Fuel Ash) PFA as solidified binder to treat
within the permissible limits. The optimum mix de- electroplating sludge. The early strength develop-
Utilization of hazardous wastes and by-products as a green concrete material through... 51

ment of lime PFA cements in the presence of 3.4. Water


Na2SiO3 and Na2CO3 was considerably higher than
The absorption capacity tends to increase with an
the strength development of those without these
increase in sludge content. This indicates that as
compounds. The maximum strength development
sludge is added, the capacity to hold water in-
was achieved at 4 and 8 wt.% dosages of Na2SiO3
creases together with a certain increase in the num-
and Na2CO3, respectively. Aluminum oxide used
ber of cavities inside the concrete. The porosity of
as a chemical admixture (10-15% by weight of ce-
the sludge resulted in the concrete having a greater
ment) is able to reduce 30% of free chloride [43].
absorption capacity. This in turn increased until the
Addition of fly ash gave measurable increase
age of 90 days, when it decreased. This is because
in strength with metakaolin (MK) [69]. MK concrete
once the concrete acquires greater hardness and
shows more loss and possessed lower residual
resistance, it requires less water and is not able to
strength as compared with other concretes [70].
assimilate it as well as it had done initially [66].
A new highly effective alkali activator like SFA
The strength of concrete is very much depen-
(Silica Fume Activator) showed high value of the
dent upon the hydration reaction just discussed.
compressive strength after 28 days curing than
Water plays a critical role, particularly the amount
used activator like sodium hydroxide, sodium car-
used. The strength of concrete increases when less
bonate, and water glass [71]. Calcium hydroxide
water is used to make concrete (Fig.2). The hy-
and ettringite, the main products of cement hydra-
dration reaction itself consumes a specific amount
tion, are characteristic products of the early ages
of water. Concrete is actually mixed with more water
of the curing process, where ettringite formation
than is needed for the hydration reactions. This
also favors the compressive strength. The best
extra water is added to give concrete sufficient
results were observed for the samples containing
workability. Flowing concrete is desired to achieve
3% CaCl2 and 2% Ca(OH)2 [61].
proper filling and composition of the forms [23].
The alkali activation of metakaolin is a way of
producing high strength cementitious materials.
The processing of these materials has been the 3.5. Engineering properties of
subject of numerous investigations. This tendency wastes and by-products bearing
was most pronounced in those samples cured in concrete
sodium sulfate solutions. This behavior may be
The performance of concrete is measured in terms
related to the change in microstructure of the
of mechanical, physical, chemical properties.
cementitious matrix of the mortars cured longer
than 90 days. Some of the amorphous material
3.5.1. Unconfined compressive
present had crystallized to a zeolite-like material
belonging to the faujasite family of zeolites [72]. strength (ucs)
Both the produced and commercial metakaolin Compressive strength development of cement
indicate a similar behavior concerning the strength paste is strongly affected by the volume of CSH
development and the corrosion resistance. The formed during cement hydration. The 28 day com-
metakaolin improves the compressive strength and pressive strengths were measured for the pastes
the 10% w/w addition shows the optimum contri- made from OPC/SF, OPC/MK, and OPC/low-cal-
bution to the strength development. The use of cium fly ash at various W/S ratios [74].
metakaolin, either as a sand replacement up to 20% The high volume fly ash (HVFA) concrete
w/w, or as a cement replacement up to 10% w/w, showed satisfactory compressive and tensile
improves the corrosion behavior of mortar speci- strength at age of 1 day. It also concluded that high
mens [73]. volume fly ash concrete showed higher strength
than OPC concrete at 28 day and beyond [53].
3.3.1. Superplasticizers Isa Yuksel and Turhan Bilir [50] suggested that
when GBFS/Sand goes beyond 30%, compression
The superplasticizers made possible to use fly ash,
strength increases again in paving block speci-
slag, silica fume, and many other industrial by-prod-
mens. As the replacement of BA/sand and GBFS/
ucts and waste materials. Addition of fly ash de-
Sand increases in between 50% and 100% substi-
creases the strength, increases the desired work-
tution ratios, compression strength value could not
ability of concrete; Superplasticizer/Cementitious
be reached in control specimen’s strength, but got
ratio of 0.015 was reported in [65].
very close results.
52 Smita Badur and Rubina Chaudhary

Concrete is one of the most important construc- results indicating that the strength decreased ap-
tion materials. It is comparatively economical, easy preciably as the proportion of sludge increased. For
to make, offers continuity and solidity, and can be all the different mixtures, the compressive strength
effectively bonded with other materials. The keys after 28 days increased in comparison with that of
to good quality concrete are the raw materials re- the previous period, but not uniformly. After 90 days,
quired to make concrete and the mix design as the compressive strength had recovered and, for
specified [24]. The test results indicated that the example, the specimens containing 10% sludge
replacement of cement with fly ash increased the reached 58% of the compressive strength of the
workability (Slump and Vebe time), decreased com- reference concrete, and those containing 2.5%
pressive strength of plain (control) concrete [65]. sludge reached 78% of the reference value [66].

3.5.2 Durability [freezing thawing 3.6. Chemical properties of wastes


resistance] and by-products bearing
Authors of [24,75] discussed strength and some concrete
durability characteristics of the concrete contain- 3.6.1. Leachability of hazardous
ing BA and high sulphate FA. The author of [50] substances
showed that usage of partially fine aggregate of
these industrial by-products has more beneficial Metal leaching from the solidified wastes was as-
effects on durability characteristics of plain con- sessed using TCLP, Acid Neutralization Capacity
crete elements. In this paper, potential usages of (ANC) and Diffusion as defined by the U.S. EPA,
BA in briquettes and GBFS in paving blocks and on the samples cured for 3, 7, 28, 90 days.
kerbs as aggregate replacement were studied. Metal concentrations in the leachates increased
Production of a new briquette type, having similar as the initial metal concentration was increasing in
properties with normal briquette but lighter than it, the solidified wastes, but there is no linear relation-
is aimed by using these byproducts and solid ship between the amount of metal leached and the
wastes. Also, development of durability properties initial concentration. The solidified waste matrices
of paving blocks and kerbs were objected. to neutralize acid were reduced. Pb, Cd, and Cu
Superplasticisers were used to improve the concentrations were below analytical detection limit
durability. Curing time and curing method affected of AAS. In addition, metal leaching from the solidi-
the durability of concrete [42,57,76]. The maximum fied wastes with 8 wt.% Na2CO3 was found in a
durability is reached when typical concrete ingre- lower concentration than from those with 4 wt.%
dients are mixed at room temperature. Therefore, Na2SiO3. This is likely because leachate pHs from
the relative amounts of the mineral phases in ce- the solidified wastes with 8 wt.% Na2CO3 ranged
ment reacted at various temperatures can be cal- between 8.4 and 9.8, being adequate to stabilize
culated. It was shown that both time and tempera- most metal hydroxides whose solubilities are
ture affect to bulk transport properties, which di- strongly pH dependent [78].
rectly influence concrete durability. For pavements, In order to assess the effectiveness of S/S, we
permeability and durability are intimately connected used the TCLP test was performed on the S/S
[29,77]. specimens. Pb and Cr concentrations in the
The main aspects of the concrete performance leachate were much lower than the respective
that will be improved by the use of fly ash are in- TCLP limits, indicating that S/S is a potential treat-
creased long-term strength and reduced perme- ment technology for refinery oily sludge. There are
ability of the concrete resulting in potentially better no TCLP limits for Cu and Ni due to lack of avail-
durability. The use of fly ash in concrete can also able data with respect to health effects and fate
address some specific durability issues such as and transport in the environment, at the time U.S.
sulphate attack and alkali silica reaction. However, regulations were passed. The TCLP extract con-
a few additional precautions have to be taken to centrations of these metals for the solidified sludge
insure that the fly ash concrete will meet all the were very low, i.e., <0.4 mg/L for Cu and <2.9 mg/
performance criteria [75]. L for Ni [64].
This study was to evaluate an alternative final Radu Barnaa et al. [73] carried out laboratory
destination for the growing production of sludge scale study on the investigation of the influence of
from sewage treatment plants. The compressive the Liquid/Solid (L/S) leaching conditions on release
strength after 7 days provided us with some clear of different chemical species from a reference po-
Utilization of hazardous wastes and by-products as a green concrete material through... 53

Water Cement Ratio


Fig. 4. Compressive strength gain with curing age of days. Data from [25].

rous material obtained by solidification of PbO and of the S/S wastes depends mainly on the type of
CdO with Portland cement. In order to determine waste and, to a lesser degree, on the type of binder
the influence of laboratory leaching conditions on agent, since cement types for each S/S waste re-
the release of different chemical species (NaC, KC, veal similar behavior to each other. The pH of the
Ca2C, Pb2C, Cd2C, and SO2K4) contained in a po- leachate produced from a S/S waste is directly af-
rous reference material obtained by solidification fected by the ANC of the waste. Since heavy metal
of PbO and CdO with Portland cement. This ap- leaching is pH dependent, the ANC test might con-
proach allowed assessing the pH influence on the stitute a rapid qualitative prediction method for po-
dissolution of pollutants and the initial pore solu- tential leaching of metals contained in the waste
tion composition were assessed by applying a [64].
methodology consisting of two equilibrium leach- The author performed time dependent diffusion
ing tests, the ANC and the Pore Water (PW) tests test. The diffusion coefficients (m) values for the
and geochemical modeling. The influence of the concretes with various replacement levels of silica
sample shape (monolithic) and elute hydrodynam- fume and slag. The results for the time dependent
ics on the leaching of the target elements was also diffusion coefficients based on total time, or mtotal
assessed. The comparison criteria were the elute values. The total time method yields the lowest m
saturation state, the cumulative release, and the value, while the effective time approach of Stanish
released flux. It would conduct that evaluate a par- and Thomas yields the highest. The initial diffu-
ticular concrete formulation before predicting its sion coefficients (28 day) are equal, but the sec-
performance in a special acid environment is nec- ondary hydration effect in concrete containing blast
essary. At least, under certain circumstances, the furnace slag leads to a greater reduction in diffu-
addition of FA, SF, or MK can improve the acid re- sion with time. The determination of diffusion coef-
sistance of concrete [74]. ficients and their time dependant behavior has an
The solidified refinery oily sludge waste sample evident effect on the estimated time to corrosion
was ground to pass a 150 mm sieve. Each sample [80,81].
was subdivided into 11 sub samples, each of 3 g in
weight. Each sub sample was placed in increasing 3.6.2. Porosity and permeability
amount of nitric acid (2N). Then the samples were
tumbled strongly at room temperature for 48 h to Permeability is closely related with strength and W/
reach equilibrium. The acid neutralizing capacity C ratio. Micro cracks in the initial stage are so small
that they may not increase the permeability. But
Table 2. Factors influencing developed concrete with differrent wastes and by-productes.

54
S. No. Type of waste Waste or Curing days Admixture Admixture % Water/Cement Waste/Binder Compressive References No.
or by-products by-products % Ratio Ratio Strength (MPa)

1. Fly ash 20 7,28 Silica fume, Metakaolin 10, 30 0.33 0.2 108-127 82 (HSC)
2. Fly ash 20 7,28 Metakaolin 20 0.40 0.2 58.4 (NSC)
3. - - 7,28 CaCl22H2O 10-30 0.36-0.40 - 1100 (kPa) 60
Ca(OH)2
4. Fly ash 16.5 g 7,28 Silica fume, Metakaolin 16.5 g 0.4,0.45 0.6,1.6 72-90 73
5. RHA, PA 10 - 30 1,3,7,28, Cr(OH)3, Fe(OH)3, >25 0.45-0.70 0.1-0.3 89.37 106
51,90,180 Zn(OH)3
6. SA, SMW 20 3,5,7,21,28, Ca(OH)2,lime stone 80 0.38 0.2-1 70-100 93
28,51,90
7. PFyA 70 1,3,5,7,21, Lime, Na2SiO3, Na2CO3 30, 4, 8 0.5 0.1-0.5 67–200 79
28.51,91
8. Fly ash 40 - 60 7,28 Superplasticizer 4.5-5.1 0.32-0.42 0.68,1,1.5 41 54 (HSC)
liters/cu.yd
9. Fly ash, Slag 57, 8 - 35 13,5,7,21,28, Silica fume 7, 8, 12 0.30±0.01 1.3,0.4,0.5, 0.08 87.5-112.3 10
51,91,151,
265-3650
10. GBFS, Fly ash 15 - 60 7,14,28 - - 0.3-0.4 0.42 15.91-51.48 51
11. GBFS, BA 20 - 50 28 Silica fume, waste glass 2.08,2.04 0.5,0.32,0.47 4.1-4.8 42.5 50
12. Electroplating 25 7, 28 Lime 10 1 0.5 35 108
sludge
13. - - 3 - 28 NaCl, Al2O3 3, 10 0.6 - 36.67 43
14. Hazardous 10, 25 28 Clay 25, 40, .45 - .65 0.1, 0.25 250 Kg/m2 104
Wastes, Fly ash 50, 90

Smita Badur and Rubina Chaudhary


15. Sludge 15 3, 7, 28 - - 0.4,0.5 0.15 Equal to control 107
16. Sludge & PFuA 0, 10, 20, 30 1-28-91 - - 0.5 0.1, 0.2, 0.3 450, 80, 42
75 Kg/m2
17. - - 3, 7, 28, 90 Silica fume, Ca(OH) 2 0 - 30 0.40 0.35, 0.4, 55, 62 109
0.45, 0.50
18. POFA 10, 20, 30, 40 28, 90, 364 Lime stone - 0.7, 0.72, 0.77, 0.1, 0.25, 30 – 37.6 110
0.87, 0.95 0.42, 1.5
19. Sludge 2.5, 5, 10 7 - 90 Melcret PF - 75 1.68 0.55 0.1 18 - 32 65
20. Fly ash, 35,45,55 28 Centriplast FF90 0.015 0.47 ± 0.02 0.35, 0.45, 0.55 26.7, 23.1 64
San fiber 0.25,0.50,0.75 (melamine formaldehyde)

Captions: HSC = High Strength Concrete, NSC = Normal Strength Concrete, EAF = Electrical Arc Furnace, BFS = Blast Furnace Slag, SA = Sludge Ash, RHA = Rice
Husk Ash, PFyA = Pulverize Fly Ash, SMW = Steel Making Waste, PA = Plating Sludge, BA = Bottom Ash, GBFS = Granulated Blast Furnace Slag, PFuA = Pulverized
Fuel Ash, GFA = Ground fly Ashes
Utilization of hazardous wastes and by-products as a green concrete material through... 55

propagation of micro cracks with time due to dry- concrete durability. ASHTO T-227 Concrete and
ing shrinkage and externally applied load will in- stripped mortar samples are taken from concrete
crease the permeability of the system [21]. Some mixtures cured for 28 days. A mortar shows higher
of the wastes and by-products also participate in chloride permeability in addition at constant cement
the structure of concrete. BA and GBFS increase content; the charges passed increase with decreas-
workability and carbonation depth and decreases ing the volume of sand in the mortar. At constant
chloride permeability [50]. cement content, there is a direct correlation be-
A model has been developed for relating po- tween the charge passed through concrete and the
rosity to permeability. It was determined that a lin- fine sand to coarse aggregate ratio. Higher W/C
ear combination of lognormal distributions can be ratio gives higher charge passage through both
used to describe pore structure. One of these dis- concretes and mortars. Chloride permeability takes
tributions describes small pores, while the remain- place primarily through the cement matrix [46]. The
ing two describe porosity through which bulk trans- effects of various pozzolans and water to cement-
port. The pore structure is very important for the ing materials ratios are clearly seen in the chloride
prediction of permeability. The results show that diffusion values presented. Initial chloride diffusion
permeability increases with temperature [70]. The values are higher in concrete mixtures at the higher
basic trend concerning the increase of porosity with water to cement ratio of 0.40 without the addition
temperature was confirmed and the values of po- of pozzolans. The chloride diffusion coefficient re-
rosity determined by both methods were closer to duces more dramatically in concrete mixtures con-
each other with an increase of temperature. The taining pozzolans showing their long-term hydra-
most dramatic increase in porosity was observed tion properties [80].
at 600 °C in mercury porosimetric measurements. The experimental work included in the current
The values of porosity at 1200 °C were the same program was directed towards assessment of re-
for the water vacuum saturation method and mer- sistance of concrete to chloride permeability. The
cury porosimetry. This indicates a significant results are expected to be useful in connection with
change of structure and disappearance of major water permeability. The technique is similar to that
cracks not detectable by mercury porosimetry [82]. described in method for measuring the chloride
According to Sandrolini and Franzoni [81], fine permeability under the effect of electric field [84].
filler effects and actual W/C ratio reduction due to
fine solids contents in sludge water leads to the 3.6.3. Sulphate corrosion
reduction of concrete capillary water absorption and
porosity, and possibly improves the durability of The S/Ca (Sulphate/Calcium) ratios are much
concrete. The porosity increased with an increase higher than those of 0.01–0.04 commonly found in
of sludge content and tends to decrease as the pastes cured at ordinary temperatures [85,86].
age of the concrete increased from 7 to 90 days. Most of the Al3+ present in the CSH appears to
The hardening of concrete has an effect of binding be primarily substituted for Si4+, [87,88] whereas
the particles, which over time, decreases the num- the sulphate incorporated into the CSH adsorbed
ber of pores [66,84]. [89]. With moist storage, sulphate can be desorbed
Poor dispersion and inhomogeneity during mix- from the CSH. The mean S/Ca ratio of the CSH
ing and placing may cause the cement particles to formed during the heat curing typically decreases
coagulate and cluster in the mix water, resulting in to values of about 0.02–0.03 during storage
alternating regions of dense and high porosity hard- [87,90,91] which is similar to that of the CSH that
ened paste, even in instances where the use of a forms later. A significant amount of sulphate was
low W/C ratio was intended to provide an ultimately taken up by the CSH during heat curing, both with
high density microstructure [85]. The water not con- mixtures containing only Portland cement as the
sumed in the hydration reaction will remain in the binder and with partial amounts of SF, MK, BFS,
microstructure pore space. These pores make the and FS. The CSH acts like a cache and this sul-
concrete weaker due to the lack of strength form- phate was later released when the specimens were
ing CSH bonds [23]. exposed to moisture at ambient temperature [92].
Higher percentages of metakaolin decrease the
corrosion resistance [73]. Sodium sulfate attack
3.6.2.1. Chloride permeability
of portland cement paste (15 mmol/l) has been
The resistance to chloride ion penetration and presented by the author. Surface abrasion is an
transport of concretes is an important feature for
56 Smita Badur and Rubina Chaudhary

important durability characteristic for paving blocks strength of the concrete is related to the water to
[50]. cement mass ratio and curing conditions. A high
The author discussed that calcium leaching in water to cement mass ratio yields a low strength
sulfate environment presents similar kinetics with concrete. This is due to the increase in porosity
respect to calcium leaching in pure de-ionized wa- (space between particles) that is created with the
ter. The precipitation of significant quantities of hydration process. Most concrete is made with
ettringite and gypsum resulted in, the breakdown water to cement mass ratio ranging from 0.35 to
of samples in presence of sulfates. Cracks were 0.6. Time is also an important factor in determin-
found predominantly in zone 2, perpendicular and ing concrete strength. Concrete hardens as time
parallel to the attacked surface, and partly filled passes. Remember that the hydration reactions get
with gypsum. The initiation of cracking and failure slower and slower as the tricalcium silicate hydrate
of the samples was found to depend significantly forms. It takes a great deal of time (even years) for
on their thickness. The proper estimation of the all of the bonds to form, which determines
service life of concrete structures to sulfate attack concrete’s strength. It is common to use a 28-day
must therefore account for these marked scale test to determine the relative strength of concrete
effects [93]. [23].

4. FACTORS AFFECTING CONCRETE 4.2. Water to cement ratio (W/C)


STRENGTH AND DURABILITY Water plays an important role in the concrete
4.1. Curing days strength. Low water to cement ratio leads to high
strength but low workability. High water to cement
Curing pathways, days and temperature, are very ratio leads to low strength, but good workability.
important factor for hardening of cement and con- The physical characteristics of aggregates are
crete. Fresh concrete gains strength most rapidly shape, texture, and size. These can indirectly af-
during the first 28 days due to hydration of cement, fect strength because they affect the workability of
which can take place only in the presence of wa- the concrete. When the water to cement mass ra-
ter. The final strength of concrete depends greatly tio is increased, the concrete will weaken [23].
on the conditions of moisture and temperature dur- Water/cement ratio showed negative effect on com-
ing this initial period. The maintenance of proper pressive strength of concrete [95,96]. The quantity
moisture and temperature conditions during this of water must not be more than 0.50 of the weight
period is known as curing. The purpose of curing of cement for most applications. Water percent-
is to prevent the loss of moisture in concrete due age also depends on the type of sand (Table 1). A
to evaporation, thereby, to prevent the development large quantity of water is highly injurious for con-
of high temperature gradient within the concrete, crete as well as steel. This is the single reason for
and hence, plastic cracking. Curing can be done in the failure or poor quality of any reinforced con-
several ways. It was concluded that high volume crete construction. More water means lesser
fly ash concrete showed higher strength than OPC strength and lesser life of concrete [20,36-40,93].
concrete at 28 day and beyond [53]. Moist curing is Abrams [96] suggested a mathematical relation-
most common. It consists of application of water ship between concrete strength and water–cement
directly to the concrete or by means of continu- ratio:
ously saturated coverings of sand, straw or hessian
bags, etc. The curing should be done for about first A
fc ′ =
−X
14 days of concreting [20,36-40]. X
= AB ,
B
Both the rate and degree of hydration, and the
resulting strength of the final concrete, depend on where, fc’ is the compressive strength of the con-
the curing process that follows in placing and con- crete, A and B are experimental parameters for a
solidating the plastic concrete (Fig. 4). By the stan- given age, material, and cure conditions, and x is
dard and other controlled conditions one can as- W/C ratio by mass:
sess curing related properties such as maturity,
shrinkage, and degree of hydration. This period W
x = ,
depends on conditions like temperature, cement C
type, and mix proportions. Degree of hydration and
CSH gel increased with the curing age [94]. The where, W is the water content and C is the cement
content [22].
Utilization of hazardous wastes and by-products as a green concrete material through... 57

G. Appa Rao [94] in discussed the water/ce- out the need to determine the degree of cement
ment ratio negative effect on compressive strength. hydration of concrete under investigation [34].
Adopted cement/sand ratios were 1:2, 1:2.5, 1:3
and the water/cement ratio was from 0.30 to 0.65. 5. DISCUSSION
The compressive strength was measured at the
age of 3, 7, 28 days. Mainly W/C ratio is influenced Landfilling is not a desirable option for the disposal
the strength of concrete. The W/C ratio described of solid hazardous waste materials. It is not a li-
the strength of concrete described by the “Abram’s able method because of future environmental costs
W/C ratio law”. Compressive strength decreases and problems associated with landfilling regulations
as the C/S ratio and the w/c ratio increases. [99]. This method increases load of toxic metals
and other contaminants in the landfill, potentially
increasing the threat to ground water contamina-
4.3. Water absorption percentage tion. Increasing economic and financial factors also
Water absorption percentage is an effective pa- dictate that industry should look forward to recy-
rameter for pure and mixed concrete. In the mixed cling and reuse of waste material as a better op-
concrete it is very important. Waste absorption tion to landfilling [100].
percentage depends on the type of waste. Water Wastes and by-products can be used in addi-
adsorption percentage increases with the increase tion to concrete without the need for large changes
of waste (Table 1)[50,63]. Water absorption re- in its preparation. Its granulometric properties indi-
duces the fine solid content and improves durabil- cate that it can be used in fine sand in production.
ity [83]. Waste content of 10% or more cannot be used
because it significantly delays the setting of the
4.4. Temperature variations cement and reduces its mechanical properties,
especially in the short term. For all waste and by-
Changes in the temperature of concrete can cause products contents, the strengths increase as the
cracking. As the concrete gets hotter, it expands; curing time of the concrete increases [66]. Some
as concrete gets cooler, it contracts similarly to waste materials have 60-90% water holding capac-
many other materials. If the concrete tends to ex- ity, which is not beneficial for concrete [50,62]. In
pand or contract, it will most likely crack [97]. the worst case the compressive strength was 4.5
Elevated temperature affects the properties of Mpa. After 28 days the same concrete had reached
concrete such as change in moisture content, de- strength of 6 MPa and after 90 days, 18 MPa, which
gree of hydration, and other features [34]. The de- would allow it to be used for road bases and sub-
gree of hydration increases with time and tempera- bases, and as a filling material [7,9,10,12,14,28].
ture, but the degree of hydration was not increased In general, it would be suitable for any application
in significant amount after 28 day curing [98]. Fly that does not require high strengths, especially not
ash/cement cured at different temperatures (20 °C in the short term [32,42,45,50]. The porosity and
and 40 °C curing temperature) shows significant the absorption coefficient increase with an increase
increase in compressive strength (Rc) of concrete in waste content and decrease as the curing time
[34,42,57]. increased [52,53,56,62]. The deformability of con-
The concrete cured at 20 °C for 28 days had a crete also increases with the increase of waste
higher degree of cement hydration and lower cap- contents [61,62,67]. The density of the concrete
illary porosity than the concrete cured in water of decreases with an increase in waste content and
the same temperature for 7 days followed by ex- increases as the curing time increases [24,69,94].
posure to outdoor air for 21 days, but had opposite With reference to our previous study on con-
trend compared to the concrete cured in 35 °C crete M15 [101] and geopolymer [99] the mixed
water for 7 days followed by exposure to outdoor concrete is a desirable option to utilize or reuse of
air. However, the differences in the degree of ce- solid hazardous waste materials. Solidified mate-
ment hydration and capillary porosity for the con- rials are weak and contain significantly less
crete cured in these different conditions were not cementitious materials and more water, for example
significant. This suggests that the reference thin concrete. Due to waste addition, CSH hydration is
sections of concrete cured at 20 °C in moist condi- poisoned. In these situations, ettringite plays an
tion for 28 days may be used to estimate the W/C important role - it increases strength and durability
of concrete cured in a tropical environment for at characteristics. UCS increases with a decrease of
least 28 days, including 7 days moist curing with- crystalline phases [91,98].
58 Smita Badur and Rubina Chaudhary

It also affects the cost of construction cement ACKNOWLEDGEMENT


and sand very important and costly material. The
The author would like to thank Dr. Kavita Kabra
replacement of them by waste and by-products
(Research Associate ar NEERI, Nagpur, India) for
gives an opportunity to manufacture economic con-
fruitful discussion. The School of Ebergy and En-
crete for the construction material.
vironmental Studies, Devi Ahilya University, Indore,
The review concluded that the developed mixed
India, is greatefully acknowledged.
concrete showed high strength, improved sulfate
resistance, decreased permeability, reduced the
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